JPH0238390A - Transfer sheet for painting and method for fixing image - Google Patents

Abstract

PURPOSE:To improve the definition, gradient and color tone and prevent the formation of pin-hole by fixing a mesh image of a painting pigment on a ground paper with a combustible photo-sensitive tacky adhesive layer interposing a paste layer between the ground paper and the adhesive layer. CONSTITUTION:A combustible photo-sensitive tacky adhesive layer 2 (e.g., layer of 2'-nitrophenyl-1,4-dihydropyridine compound) is applied to a paste layer 4 formed on a ground paper 3. An image is applied and fixed to the adhesive layer in mesh pattern with a painting pigment 1 containing an inorganic compound (e.g., CoO) and optionally <=30% of glass frits having particle diameter of <=8mum. A combustible film 5 is attached to the image to obtain the objective sheet.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a transfer sheet for painting ceramic products such as ceramics and glass, which can still achieve the same resolution as a normal photograph even after firing. The present invention relates to a new transfer sheet that can maintain images with good gradation and color reproducibility, and an image fixing method therefor.

[Conventional technology and its problems] Designs fired onto ceramics such as china and glass are durable and durable, as is clear from the fact that they have been excavated from ruins thousands of years ago with the same color as when they were made. Excellent weather resistance.

In other words, the method of drawing an image on ceramics and firing it is an ideal method for fixing the image for a long period of time.You can print art paintings, photographs, maps, publications, etc. onto ceramics or glass and preserve them for a long time. There is a strong desire to leave it in a stable condition.

However, painting on ceramics and glass is usually done by handwriting directly on the material or by transferring the picture onto the material using transfer paper created by screen printing.

Hand-painted paper is inferior in terms of color and shape reproducibility, resolution, and mass production.Screen printing, although excellent in mass production, is far behind photography in terms of resolution, gradation, and color reproducibility. .

The reason for this is: - Because the process involves applying ink through the mesh of the screen, the resolution is at most 1
■Furthermore, as the strong force of the squeegee is applied during printing and the screen film itself is greatly deformed, it is essential to perform highly accurate positioning when overprinting colors. There are some difficult things.

In addition, screen printing does not have enough resolution to subtly express the area differences of halftone dots even when expressing one gradation, making it difficult to express continuous gradations like normal printing. .

In addition, there is a risk that color development may change due to chemical reactions between pigments during firing due to overlapping of colors due to lack of printing precision.

In order to compensate for this, it is common practice to print many colors in addition to the three primary colors to create complementary colors, which leads to a vicious cycle that further reduces resolution and gradation.

Furthermore, it is difficult to form a thin film with screen printing, and as a result, the pattern after firing is inevitably thicker, has an unnatural shine, and has irregularities corresponding to the pattern, and when compared to photographs, it is difficult to form a thin film. It was difficult to avoid creating an unnatural pattern that was unique and reminiscent of pottery.

For this reason, it was not possible to vividly fire detailed designs like photographs; realistic images onto ceramics or glass.

Therefore, we used offset printing, which has better resolution and printing accuracy than screen printing, to create a plate with the color-separated image, and used this plate to print the ink for the illustration onto the mount for the transfer paper. It is done in some places.

However, because the cost of the plate is high, it is not cost-effective unless it is produced in large quantities, and because the amount of pigment contained in the ink is limited, the color development is poor and only pale-toned designs can be fired. .

It takes time and time to dry the offset oil, and especially in the case of multicolor printing, it takes too many days to be practical.

In addition, in order to improve color development, instead of incorporating pigment into the ink, a method is used to print a pattern with glue and then sprinkle the pigment on top of it to fix it. It is not generally used because of the cost and drying time.

Furthermore, if a transfer paper is made by layering pigments of different colors, such as color photographs, fixed to a flammable photosensitive adhesive layer and pasted on an object, when it burns, the most If the lower adhesive layer burns first, the cracked gas causes foaming, which causes problems such as peeling of the pigment pattern located above it and formation of pinholes.

[Means for Solving the Problems] Therefore, the main object of the present invention is to provide a new transfer paper and a method for fixing images thereon that solves the above-mentioned problems in the conventional technology. In detail, firstly, we provide transfer paper with good color reproducibility, secondly, we provide transfer paper with high resolution and gradation, and thirdly, we provide transfer paper with excellent contrast. The fourth purpose is to produce transfer paper for such decoration at low cost even in small quantities.

To do this, we first focused on the functions of photosensitive adhesives, and used photography to form an image using light beams on the flammable photosensitive adhesive layer, and the adhesiveness changed locally in accordance with the image. After that, an inorganic compound or a pigment containing glass frit is selectively applied to the flammable photosensitive adhesive layer to fix the image, and the image on the transfer paper is fixed. At the time of formation, the image is made up of halftone dots, whereby a photosensitive adhesive is used to expose the digital image made up of the halftone dots and convert it into tacky or non-tacky form. Accordingly, pigments are selectively applied to only the adhesive areas to fix the image.

According to the present invention, in this manner, a pattern can be fired using a transfer paper on which a single color (monochrome) or multicolor (color) image is freely fixed.

To fire a color image, halftone photographic film made for each of the three primary colors is used, the image is fixed to a flammable photosensitive adhesive, and the images are precisely pasted together using a suitable alignment mechanism to create a transfer sheet. It's fine.

By doing this, it is possible to fix the image on the transfer paper without preparing special plates required for screen printing or offset printing, making it possible to achieve low-cost production even in small quantities. .

Furthermore, in the present invention, once a transfer paper with a fixed monochrome or multicolor image is created in this way, after that,
Its unique feature is that it can create detailed images on ceramics and glass products that are as detailed as photographs, using the same processes commonly used in the traditional ceramic industry.

The photosensitive adhesive in this invention is a photocurable adhesive that is cured by irradiation with light and loses its adhesiveness,
On the contrary, it is a photosensitive adhesive material that exhibits adhesiveness only in the area exposed to light, and is also excellent in flammability and dimensional stability at high temperatures.

Examples thereof include bisimidazole compounds, dihydropyridine compounds, and the like.

The light used to form photographic halftone dots by exposing the adhesive layer to light includes infrared rays, visible light, ultraviolet rays, X-rays, and electron beams, but it is possible to work in a bright room. Considering the practicality of low equipment cost,
Adhesives that react to ultraviolet light are preferred.

The most preferred example of such an adhesive is a 2°nitrophenyl-1,4-dihydropyridine compound.

In addition, since the adhesive is in the form of a thin layer, during the exposure, pigment adhesion, and layering processes, acrylic or nitrocellulose, etc., are used to hold it in place so that no carbon components are left behind when burned, and the adhesive shrinks. Preferably, at least one surface is coated with a film made of a material that does not easily cause cracks.

This holding film may be used as a base of a transfer sheet, or it may be incinerated together with the adhesive layer at the same time as the adhesive layer without peeling off the film.

As the pigment, those commonly used for painting ceramics and glass may be used.

For example, any known red pigment containing at least one of metals such as iron, chromium, copper, gold, and selenium can be used, as well as metal powders such as iron, copper, gold, and silver. is Mn0-AI, O>, Cr20y
SnO2, Fe:03CdS-3eS, etc. can be mentioned.

Further, as the blue pigment, any known pigment containing at least one of metals such as copper, manganese, iron, and cobalt can be used, and specific examples thereof include Coo, ZrO2-v
20t, cr20. -v20, etc. Any known black pigment containing at least one of metals such as iron, manganese, copper, chromium, and cobalt can be used, and specific examples thereof include, for example, Cr 20
゜Coo Fe, Ox Mn0z, etc. can be mentioned.

Or spinel-type brown, black, blue-green, alumina-type green-black, garnet-type Victoria green, chrome-tin pink, navel yellow, vanadium-tin yellow, whose main components are iron oxide and chromium oxide. , vanadium tin titanium yellow, antimony tin gray, and those containing zirconium oxide as a main component include metal oxides such as vanadium zirconium yellow, vanadium yttrium zirconium orange, and chromium titanium yellow containing titanium oxide as a main component.

Various pigments made of these metals or inorganic compounds made of metal oxides can be used as they are, but if necessary, glass frit as an adhesive may be included.

However, since the amount of pigment attached decreases accordingly, in order to increase the color density and obtain a high gradation, it is desirable to suppress the glass component to 30% or less based on the total amount.

If the image does not contain a glass component, it is not possible to fix the image to the substrate as it is, but there are methods to melt the pigment into the glass as a glaze for the object, or to coat the pattern with frit glass. It can be easily fixed by the method of fixing.

In order to increase the resolution of the image and enhance the gradation expression,
The particle size of these pigments is preferably as small as possible, with an average particle size of 8 μm or less, particularly 5 μm or less.

In addition, in the case of multicolor printing, the pigments of each color interact with each other during firing.
It is desirable to choose a combination that will cause as few changes in color as possible due to chemical reactions.

In order to prevent peeling of the pigment pattern and generation of pinholes during firing, the combustion temperature of the flammable photosensitive adhesive on the side closer to the object when transferred is higher than that on the side far from the object. The type of flammable photosensitive adhesive may be changed so that the combustion temperature is higher than the combustion temperature of the flammable photosensitive adhesive.

Further, the halftone image in the present invention is obtained by modulating the continuous tone image of the R draft by a glass screen method, a contact screen method, a scanning imaging method, or the like.

The number of screen lines is 1. It is preferable to set the density to OO line/inch or more, but it is better to set the screen line so that it is not smaller than the particle size of the pigment.

[Example] The present invention will be explained in detail below.

Example 1 (For monochrome photography) First, a photosensitive adhesive containing a 2'-nitrophenyl-1,4-dihydropyridine compound was applied to a thickness of 2μ on one side of a nitrocellulose film with good combustibility. A separately prepared screen line count of 133 was added to the film created by
By irradiating ultraviolet rays with a wavelength of around 500 nm through a negative photographic film subjected to halftone dot processing of /inch, the exposed portions were made sticky.

Next, a black pigment containing chromium oxide as the main component is sprinkled onto the adhesive layer, and by removing the excess pigment, the black pigment adheres to the sticky area, that is, the exposed area. did.

A thin layer of water-soluble glue was then applied onto the paper.

By laminating the acrylic film on top of the water transfer paper, the water transfer paper was completed.

After that, the film was peeled off from the mount using the usual water transfer paper method, transferred to the surface of a mug, and baked at 800℃ for 30 minutes. The pigments imprinted a predetermined image onto the mug.

Example 2 (in the case of a color photo) First, from the color photo you want to print, prepare original film for 4 colors (yellow, magenta, cyan, black) that has been subjected to color separation and halftone processing. , four sheets were prepared with pigments of each color attached.

Next, four photosensitive adhesive films were sequentially stacked on top of each other while positioning them using appropriately provided marks, and a combustible film was laminated on top to prevent pigment scattering.

Apply 5μ of glue to one side of the film made in this way,
A transfer sheet was created for the illustrations.

This sheet was attached directly to a ceramic plate using a glue, heated from room temperature to 800'C at a rate of 20'C/10 minutes, and then fired at 800°C for 20 minutes. After the photosensitive adhesive film layer that fixes the image is burned, the adhesive layer at the bottom is burned, so there is no movement of the pattern or generation of pinholes due to foaming caused by decomposed gas, and it is no different from normal color photography. A pattern with high resolution and color tone was formed on the ceramic plate.

[Effects of the invention] By using the transfer method, which has traditionally been a common method of painting, it is possible to create designs on ceramics and glass that have the same resolution, gradation, and color tone as ordinary photographs or offset printing. It is now possible to print on ceramic materials such as without abnormal gloss or pinholes.

This makes it possible to make the durability of exhibits that are exposed to the outdoors for long periods of time almost semi-permanent, and also to preserve the durability of personal photographs, valuable art paintings, publications, etc., for future generations.
Now you can leave it in its original color and shape.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of essential parts showing an embodiment of transfer paper for monochrome photographs according to the present invention, and FIG. FIG.

Claims (5)

[Claims] (1) A transfer sheet for painting on ceramics or glass products, etc., in which an image is fixed on a mount via a glue layer with a painting pigment containing an inorganic compound or the same and glass frit. The image created by pigments is
A transfer sheet for painting, comprising halftone dots and fixed by a flammable photosensitive adhesive layer. (2) A transfer sheet for decoration according to claim (1), characterized in that a pigment for decoration is used which has a particle size of 8 μm or less and a proportion of a glass component contained in the pigment is 30% or less. . (3) By attaching a painting pigment containing an inorganic compound or a glass frit to a flammable photosensitive adhesive through a glue layer on a mount, a layer with a fixed image can be created in different colors. , a transfer sheet for painting that is characterized by being laminated with multiple layers. (4) In the transfer sheet for painting according to claim (3), the combustion temperature of the layer closer to the object when transferred is
A transfer sheet for painting that has a higher combustion temperature than the layer on the side far from the object. (5) forming an image with a light beam onto the flammable photosensitive adhesive layer supported by the substrate, and
changing the adhesion locally in accordance with the image, and then selectively attaching an inorganic compound or a painting pigment containing the same and glass frit to the flammable photosensitive adhesive layer;
A method for fixing an image on a transfer sheet for painting, characterized by fixing an image.